Organometal catalyst compositions

ABSTRACT

This invention provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer. This invention also provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer, wherein said catalyst composition comprises a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted treated solid oxide compound.

FIELD OF THE INVENTION

[0001] This invention is related to the field of organometal catalystcompositions.

BACKGROUND OF THE INVENTION

[0002] The production of polymers is a multi-billion dollar business.This business produces billions of pounds of polymers each year.Millions of dollars have been spent on developing technologies that canadd value to this business.

[0003] One of these technologies is called metallocene catalysttechnology. Metallocene catalysts have been known since about 1960.However, their low productivity did not allow them to be commercialized.About 1975, it was discovered that contacting one part water with onepart trimethylalurninum to form methyl alurninoxane, and then contactingsuch methyl aluminoxane with a metallocene compound, formed ametallocene catalyst that had greater activity. However, it was soonrealized that large amounts of expensive methyl aluminoxane were neededto form an active metallocene catalyst. This has been a significantimpediment to the commercialization of metallocene catalysts.

[0004] Borate compounds have been used in place of large amounts ofmethyl aluminoxane. However, this is not satisfactory, since boratecompounds are very sensitive to poisons and decomposition, and can alsobe very expensive.

[0005] It should also be noted that having a heterogeneous catalyst isimportant. This is because heterogeneous catalysts are required for mostmodem commercial polymerization processes. Furthermore, heterogeneouscatalysts can lead to the formation of substantially uniform polymerparticles that have a high bulk density. These types of substantiallyuniformed particles are desirable because they improve the efficiency ofpolymer production and transportation. Efforts have been made to produceheterogeneous metallocene catalysts; however, these catalysts have notbeen entirely satisfactory.

[0006] Therefore, the inventors provide this invention to help solvethese problems.

SUMMARY OF THE INVENTION

[0007] An object of this invention is to provide a process that producesa catalyst composition that can be used to polymerize at least onemonomer to produce a polymer.

[0008] Another object of this invention is to provide the catalystcomposition.

[0009] Another object of this invention is to provide a processcomprising contacting at least one monomer and the composition underpolymerization conditions to produce the polymer.

[0010] Another object of this invention is to provide an article thatcomprises the polymer produced with the catalyst composition of thisinvention.

[0011] In accordance with one embodiment of this invention, a process toproduce a catalyst composition is provided. The process comprises (oroptionally, “consists essentially of”, or “consists of”) contacting anorganometal compound, an organoalurninum compound, and a treated solidoxide compound to produce the catalyst composition;

[0012] wherein the organometal compound has the following generalformula:

(X¹)(X²)(X³)(X⁴)M¹

[0013] wherein M¹ is selected from the group consisting of titanium,zirconium, and hafnium;

[0014] wherein (X¹) is independently selected from the group consistingof cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls;

[0015] wherein substituents on the substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls of (X¹) are selectedfrom the group consisting of aliphatic groups, cyclic groups,combinations of aliphatic and cyclic groups, silyl groups, alkyl halidegroups, halides, organometallic groups, phosphorus groups, nitrogengroups, silicon, phosphorus, boron, germanium, and hydrogen;

[0016] wherein at least one substituent on (X¹) can be a bridging groupwhich connects (X¹) and (X²);

[0017] wherein (X3) and (X⁴) are independently selected from the groupconsisting of halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;

[0018] wherein (X²) is selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, substituted fluorenyls, halides, aliphatic groups,substituted aliphatic groups, cyclic groups, substituted cyclic groups,combinations of aliphatic groups and cyclic groups, combinations ofsubstituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, amidogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkyloxide groups, substituted alkyloxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups;

[0019] wherein substituents on (X²) are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticgroups and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

[0020] wherein at least one substituent on (X²) can be a bridging groupwhich connects (X¹) and (X²);

[0021] wherein the organoaluminum compound has the following generalformula:

Al(X⁵)_(n)(X⁶)_(3−n)

[0022] wherein (X⁵) is a hydrocarbyl having from 1-20 carbon atoms;

[0023] wherein (X⁶) is a halide, hydride, or alkoxide;

[0024] wherein “n” is a number from 1 to 3 inclusive; and

[0025] wherein the treated solid oxide compound comprises nickel, ahalogen, and a solid oxide compound;

[0026] wherein the halogen is selected from the group consisting ofchlorine and bromine;

[0027] wherein the solid oxide compound is selected from the groupconsisting of alumina, aluminophosphate, aluminosilicate, and mixturesthereof.

[0028] In accordance with another embodiment of this invention, aprocess is provided comprising contacting at least one monomer and thecatalyst composition under polymerization condition to produce apolymer.

[0029] In accordance with another embodiment of this invention, anarticle is provided. The article comprises the polymer produced inaccordance with this invention.

[0030] These objects, and other objects, will become more apparent tothose with ordinary skill in the art after reading this disclosure.

DETAILED DESCRIPTION OF THE INVENTION

[0031] Organometal compounds used in this invention have the followinggeneral formula:

(X¹)(X²)(X³)(X⁴)M¹

[0032] In this formula, M¹ is selected from the group consisting oftitanium, zirconium, and hafnium. Currently, it is most preferred whenM¹ is zirconium.

[0033] In this formula, (X¹) is independently selected from the groupconsisting of (hereafter “Group OMC-I”) cyclopentadienyls, indenyls,fluorenyls, substituted cyclopentadienyls, substituted indenyls, suchas, for example, tetrahydroindenyls, and substituted fluorenyls, suchas, for example, octahydrofluorenyls.

[0034] Substituents on the substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls of (X¹) can be selectedindependently from the group consisting of aliphatic groups, cyclicgroups, combinations of aliphatic and cyclic groups, silyl groups, alkylhalide groups, halides, organometallic groups, phosphorus groups,nitrogen groups, silicon, phosphorus, boron, germanium, and hydrogen, aslong as these groups do not substantially, and adversely, affect thepolymerization activity of the composition.

[0035] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefms. Suitable examples of cyclic groupsare cycloparaffms, cycloolefms, cycloacetylenes, and arenes. Substitutedsilyl groups include, but are not limited to, alkylsilyl groups whereeach alkyl group contains from 1 to about 12 carbon atoms, arylsilylgroups, and arylalkylsilyl groups. Suitable alkyl halide groups havealkyl groups with 1 to about 12 carbon atoms. Suitable organometallicgroups include, but are not limited to, substituted silyl derivatives,substituted tin groups, substituted germanium groups, and substitutedboron groups.

[0036] Suitable examples of such substituents are methyl, ethyl, propyl,butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl,octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl,chloro, bromo, iodo, trimethylsilyl, and phenyloctylsilyl.

[0037] In this formula, (X³) and (X⁴) are independently selected fromthe group consisting of (hereafter “Group OMC-II”) halides, aliphaticgroups, substituted aliphatic groups, cyclic groups, substituted cyclicgroups, combinations of aliphatic groups and cyclic groups, combinationsof substituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic and substituted cyclic groups, amido groups,substituted amido groups, phosphido groups, substituted phosphidogroups, alkyloxide groups, substituted alkyloxide groups, aryloxidegroups, substituted aryloxide groups, organometallic groups, andsubstituted organometallic groups, as long as these groups do notsubstantially, and adversely, affect the polymerization activity of thecomposition.

[0038] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefms. Suitable examples of cyclic groupsare cycloparaffms, cycloolefms, cycloacetylenes, and arenes. Currently,it is preferred when (X³) and (X⁴) are selected from the groupconsisting of halides and hydrocarbyls, where such hydrocarbyls havefrom 1 to about 10 carbon atoms. However, it is most preferred when (X³)and (X⁴) are selected from the group consisting of fluoro, chloro, andmethyl.

[0039] In this formula, (X²) can be selected from either Group OMC-I orGroup OMC-II.

[0040] At least one substituent on (X¹) or (X²) can be a bridging groupthat connects (X¹) and (X²), as long as the bridging group does notsubstantially, and adversely, affect the activity of the composition.Suitable bridging groups include, but are not limited to, aliphaticgroups, cyclic groups, combinations of aliphatic groups and cyclicgroups, phosphorous groups, nitrogen groups, organometallic groups,silicon, phosphorus, boron, and germamum.

[0041] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefms. Suitable examples of cyclic groupsare cycloparaffms, cycloolefms, cycloacetylenes, and arenes. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

[0042] Various processes are known to make these organometal compounds.See, for example, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305;5,401,817; 5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636;5,565,592; 5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284;5,554,795; 5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203;5,654,454; 5,705,579; and 5,668,230; the entire disclosures of which arehereby incorporated by reference.

[0043] Specific examples of such organometal compounds are as follows:

[0044] bis(cyclopentadienyl)hafnium dichloride;

[0045] bis(cyclopentadienyl)zirconium dichloride;

[0046] 1,2-ethanediylbis(η⁵- 1 -indenyl)di-n-butoxyhafnium;

[0047] 1,2-ethanediylbis(η⁵- 1 -indenyl)dimethylzirconium;

[0048] 3,3 -pentanediylbis(η⁵- 4,5,6,7-tetrahydro-1-indenyl)hafniumdichloride;

[0049] methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

[0050] bis(n-butylcyclopentadienyl)bis(di-t-butylamido)hafinium;

[0051] bis(n-butylcyclopentadienyl)zirconium dichloride;

[0052] dimethylsilylbis(1-indenyl)zirconium dichloride;

[0053] octylphenylsilylbis(1-indenyl)hafnium dichloride;

[0054] ditnethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

[0055] dimethylsilylbis(2-methyl-1-indenyl)zircomum dichloride;

[0056] 1,2-ethanediylbis(9-fluorenyl)zirconium dichloride;

[0057] indenyl diethoxy titanium(IV) chloride;

[0058] (isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride;

[0059] bis(pentamethylcyclopentadienyl)zircomum dichloride;

[0060] bis(indenyl) zirconium dichloride;

[0061] methyloctylsilyl bis (9-fluorenyl) zirconium dichloride;

[0062] bis-[1-(N,N-diisopropylarnino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate

[0063] Preferably, the organometal compound is selected from the groupconsisting of

[0064] bis(n-butylcyclopentadienyl)zirconium dichloride;

[0065] bis(indenyl)zirconium dichlonrde;

[0066] dimethylsilylbis(1-indenyl) zirconium dichloride;

[0067] methyloctylsilylbis(9-fluorenyl)zirconium dichloride

[0068] Organoaluminum compounds have the following general formula:

Al(X⁵ )_(n)(X⁶)_(3−n)

[0069] In this formula, (X⁵) is a hydrocarbyl having from 1 to about 20carbon atoms. Currently, it is preferred when (X⁵) is an alkyl havingfrom 1 to about 10 carbon atoms. However, it is most preferred when (X⁵)is selected from the group consisting of methyl, ethyl, propyl, butyl,and isobutyl.

[0070] In this formula, (X⁶) is a halide, hydride, or alkoxide.Currently, it is preferred when (X⁶) is independently selected from thegroup consisting of fluoro and chloro. However, it is most preferredwhen (X⁶) is chloro.

[0071] In this formula, “n” is a number from 1 to 3 inclusive. However,it is preferred when “n” is 3.

[0072] Examples of such compounds are as follows:

[0073] trimethyl aluminum;

[0074] triethylaluminum (TEA);

[0075] tripropylaluminum;

[0076] diethylaluminum ethoxide;

[0077] tributylaluminum;

[0078] diisobutylaluminum hydride;

[0079] triisobutylaluminum hydride;

[0080] triisobutylaluminum; and

[0081] diethylaluminum chloride.

[0082] Currently, TEA is preferred.

[0083] The treated solid oxide compound comprises nickel, a halogen, anda solid oxide compound. The halogen is selected from the groupconsisting of chlorine and bromine. The solid oxide compound is selectedfrom the group consisting of alumina, aluminophosphate, aluminosilicate,and mixtures thereof Preferably, the solid oxide compound is alumina.

[0084] The solid oxide compound should have a pore volume greater thanabout 0.5 cc/g, preferably greater than about 0.8 cc/g, and mostpreferably, greater than 1.0 cc/g.

[0085] The solid oxide compound should have a surface area in a range ofabout 100 to about 1000 m²/g, preferably from about 200 to about 800m²/g, and most preferably, from 250 to 600 m²/g.

[0086] To produce the treated solid oxide compound, the solid oxidecompound is treated with a nickel-containing compound, in order to addnickel to the solid oxide compound. Nickel can be added to the solidoxide compound by any method known in the art. In a first method, nickelcan be added to the solid oxide compound by cogellation of aqueousmaterials, as disclosed in U.S. Pat. Nos. 3,887,494; 3,119,569;4,405,501; 4,436,882; 4,436,883; 4,392,990; 4,081,407; 4,981,831; and4,152,503; the entire disclosures of which are hereby incorporated byreference. In a second method, the nickel can be added to the solidoxide compound by cogellation in an organic or anhydrous solution asdisclosed in U.S. Pat. Nos. 4,301,034; 4,547,557; and 4,339,559; theentire disclosures of which are hereby incorporated by reference. Thepreferred method is to impregnate the solid oxide compound with anaqueous or organic solution of a nickel-containing compound prior tocalcining to produce a nickel-containing solid oxide compound. Asuitable amount of the solution is utilized to provide the desiredconcentration of nickel after drying. The nickel-containing solid oxidecompound is then dried by any suitable method known in the art. Forexample, the drying can be accomplished by vacuum drying, spray drying,or flash drying.

[0087] Any nickel-containing compound known in the art that canimpregnate the solid oxide compound with nickel can be used in thisinvention. The nickel-containing compound can be any water solublenickel salt, such as, for example, nickel nitrate, nickel chloride,nickel sulfate, nickel acetate, or nickel citrate. The nickel-containingcompound can also be an organic nickel compound, such as, for example,nickel acetylacetonate, nickel ethylhexanoate, nickel naphthenate, andmixtures thereof.

[0088] Generally, the amount of nickel present is in the range of about0.1 to about 10 millimoles per gram of nickel-containing solid oxidecompound before calcining. Preferably, the amount of nickel present isin the range of about 0.5 to about 5 millimoles per gram ofnickel-containing solid oxide compound before calcining. Mostpreferably, the amount of nickel present is in the range of 1 to 3millimoles per gram of nickel-containing solid oxide compound beforecalcining.

[0089] After the solid oxide compound is combined with thenickel-containing compound to produce a nickel-containing solid oxidecompound, it is then calcined for about 1 minute to about 100 hours,preferably for about 1 hour to about 50 hours, and most preferably, from3 hours to 20 hours. The calcining is conducted at a temperature in arange of about 200 to about 900° C., preferably, in a range of about 300to about 800° C., and most preferably, in a range of 400 to 700° C. Anytype of suitable ambient can be used during calcining. Generally,calcining can be completed in an inert atmosphere. Alternatively, anoxiding atmosphere, such as, for example, oxygen or air, or a reducingatmosphere, such as, for example, hydrogen or carbon monoxide, can beused.

[0090] After or during calcming, the nickel-containing solid oxidecompound is contacted with a halogen-containing compound to produce thetreated solid oxide compound. The halogen-containing compound is atleast one compound selected from the group consisting ofchloride-containing compounds and bromide-containing compounds. Thehalogen-containing compound can be in a liquid or preferably, a vaporphase. The nickel-containing solid oxide compound can be contacted withthe halogen-containing compound by any means known in the art.Preferably, the halogen-containing compound can be vaporized into a gasstream used to fluidize the solid oxide compound during calcining. Thenickel-containing solid oxide compound is contacted with thehalogen-containing compound generally from about 1 minute to about 10hours, preferably, from about 5 minutes to about 2 hours, and mostpreferably, from 10 minutes to 30 minutes. Generally, thenickel-containing solid oxide compound is in contact with thehalogen-containing compound at a temperature in the range of about 200to about 900° C., preferably, at a temperature in a range of about 300to about 800° C., and most preferably, in a range of 400 to 700° C. Anytype of suitable ambient can be used to contact the nickel-containingsolid oxide compound and the halogen-containing compound. Preferably, aninert atmosphere is used. Alternatively, an oxiding or reducingatmosphere can also be used.

[0091] Suitable halogen-containing compounds include volatile or liquidorganic chloride or bromide compounds and inorganic chloride or bromidecompounds. Organic chloride or bromide compounds can be selected fromthe group consisting of carbon tetrachloride, chloroform,diclloroethane, hexachlorobenzene, trichloroacetic acid, bromoform,dibromomethane, perbromopropane, and mixtures thereof. Inorganicchloride or bromide compounds can be selected from the group consistingof gaseous hydrogen chloride, silicon tetrachloride, tin tetrachloride,titanium tetrachloride, aluminum trichloride, boron trichloride, thionylchloride, suflfiryl chloride, hydrogen bromide, boron tribromide,silicon tetrabrornide, and mixtures thereof. Additionally, chlorine andbromine can be used. Optionally, a fluorine-containing compound can alsobe included when contacting the nickel-containing solid oxide compoundwith the halogen-containing compound to achieve higher activity in somecases.

[0092] The amount of halogen present in the treated solid oxide compoundis generally in the range of about 2 to about 150% by weight, preferablyabout 10% to about 100% by weight, and most preferably, 15% to 75% byweight, where the weight percents are based on the weight of the treatedsolid oxide compound before calcining.

[0093] The compositions of this invention can be produced by contactingthe organometal compound, the treated solid oxide compound, and theorganoalumnum compound, together. This contacting can occur in a varietyof ways, such as, for example, blending. Furthermore, each of thesecompounds can be fed into the reactor separately, or variouscombinations of these compounds can be contacted together before beingfurther contacted in the reactor, or all three compounds can becontacted together before being introduced into the reactor.

[0094] Currently, one method is to first contact an organometal compoundand the treated solid oxide compound together, for about 1 minute toabout 24 hours, preferably, about 1 minute to about 1 hour, at atemperature from about 10° C. to about 100° C., preferably 15° C. to 50°C., to form a first mixture, and then contact this first mixture with anorganoaluminum compound to form the catalyst composition.

[0095] Another method is to precontact the organometal compound, theorganoaluminum compound, and the treated solid oxide compound beforeinjection into a polymerization reactor for about 1 minute to about 24hours, preferably, 1 minute to 1 hour, at a temperature from about 10ICto about 200° C., preferably 20° C. to 80° C. to produce the catalystcomposition.

[0096] A weight ratio of the organoaluminum compound to the treatedsolid oxide compound in the composition ranges from about 5:1 to about1:1000, preferably, from about 3:1 to about 1:100, and most preferably,from 1:1 to 1:50.

[0097] A weight ratio of the treated solid oxide compound to theorganometal compound in the composition ranges from about 10,000:1 toabout 1:1, preferably, from about 1000:1 to about 10:1, and mostpreferably, from 250:1 to 20:1. These ratios are based on the amount ofthe components combined to give the catalyst composition.

[0098] After contacting, the composition comprises a post-contactedorganometal compound, a post-contacted organoaluminum compound, and apost-contacted treated solid oxide compound. It should be noted that thepost-contacted solid oxide compound is the majority, by weight, of thecomposition. Often times, specific components of a catalyst are notknown, therefore, for this invention, the composition is described ascomprising post-contacted compounds.

[0099] A weight ratio of the post-contacted organoaluminum compound tothe post-contacted treated solid oxide compound in the compositionranges from about 5:1 to about 1:1000, preferably, from about 3:1 toabout 1:100, and most preferably, from 1:1 to 1:50.

[0100] A weight ratio of the post-contacted treated solid oxide compoundto the post-contacted organometal compound in the composition rangesfrom about 10,000:1 to about 1:1, preferably, from about 1000:1 to about10:1, and most preferably, from 250:1 to 20:1.

[0101] The composition of this invention has an activity greater than acomposition that uses the same organometal compound, and the sameorganoaluminum compound, but uses silica, alumina, or a chloridedalumina that has not been impregnated with nickel as an activator forthe organometal compound as shown in comparative examples 1-3. Theactivity is measured under slurry polymerization conditions, usingisobutane as the diluent, and with a polymerization temperature of about50 to about 110° C., and an ethylene pressure of about 400 to about 800psig. When comparing activities, the polymerization runs should occur atthe same polymerization conditions. The reactor should havesubstantially no indication of any wall scale, coating or other forms offouling.

[0102] However, it is preferred if the activity is greater than about1000 grams of polymer per gram of treated solid oxide compound per hour,more preferably greater than about 2000, and most preferably greaterthan 3000. This activity is measured under slurry polymerizationconditions, using isobutane as the diluent, and with a polymerizationtemperature of 900° C., and an ethylene pressure of 550 psig. Thereactor should have substantially no indication of any wall scale,coating or other forms of fouling.

[0103] One of the important aspects of this invention is that noaluminoxane needs to be used in order to form the composition.Aluminoxane is an expensive compound that greatly increases polymerproduction costs. This also means that no water is needed to help formsuch aluminoxanes. This is beneficial because water can sometimes kill apolymerization process. It should be noted that no fluorophenyl borateor other fluoroorganic boron compounds need to be used in order to formthe catalyst composition. In summary, this means that the catalystcomposition, which is heterogenous, and which can be used forpolymerizing monomers, can be easily and inexpensively produced becauseof the substantial absence of any aluminoxane compounds or boratecompounds. Additionally, no organochromium compounds or MgCl₂ need to beadded to form the invention. Although aluminoxane, fluoroorganic boroncompounds, organochromium compounds, or MgCl₂ are not needed in thepreferred embodiments, these compounds can be used in other embodimentsof this invention.

[0104] In another embodiment of this invention, a process comprisingcontacting at least one monomer and the catalyst composition to produceat least one polymer is provided. The term “opolymer” as used in thisdisclosure includes homopolymers and copolymers. The catalystcomposition can be used to polymerize at least one monomer to produce ahomopolymer or a copolymer. Usually, homopolymers are comprised ofmonomer residues, having 2 to about 20 carbon atoms per molecule,preferably 2 to about 10 carbon atoms per molecule. Currently, it ispreferred when at least one monomer is selected from the groupconsisting of ethylene, propylene, 1-butene, 3-methyl-1-butene,1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,3-ethyl-i-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixturesthereof.

[0105] When a homopolymer is desired, it is most preferred to polymerizeethylene or propylene. When a copolymer is desired, the copolymercomprises monomer residues and one or more comonomer residues, eachhaving from about 2 to about 20 carbon atoms per molecule. Suitablecomonomers include, but are not limnited to, aliphatic 1-olefms havingfrom 3 to 20 carbon atoms per molecule, such as, for example, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and otherolefms and conjugated or nonconjugated diolefms such as 1,3-butadiene,isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene,1,7-hexadiene, and other such diolefms and mixtures thereof. When acopolymer is desired, it is preferred to polymerize ethylene and atleast one comonomer selected from the group consisting of 1-butene,1-pentene, 1-hexene, 1-octene, and 1-decene. The amount of comonomerintroduced into a reactor zone to produce a copolymer is generally fromabout 0.01 to about 10 weight percent comonomer based on the totalweight of the monomer and comonomer, preferably, about 0.01 to about 5,and most preferably, 0.1 to 4. Alternatively, an amount sufficient togive the above described concentrations, by weight, in the copolymerproduced can be used.

[0106] Processes that can polymerize at least one monomer to produce apolymer are known in the art, such as, for example, slurrypolymerization, gas phase polymerization, and solution polymerization.It is preferred to perform a slurry polymerization in a loop reactionzone. Suitable diluents used in slurry polymerization are well known inthe art and include hydrocarbons which are liquid under reactionconditions. The term “diluent” as used in this disclosure does notnecessarily mean an inert material; it is possible that a diluent cancontribute to polymerization. Suitable hydrocarbons include, but are notlimited to, cyclohexane, isobutane, n-butane, propane, n-pentane,isopentane, neopentane, and n-hexane. Furthermore, it is most preferredto use isobutane as the diluent in a slurry polymerization. Examples ofsuch technology can be found in U.S. Pat. Nos. 4,424,341; 4,501,885;4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which arehereby incorporated by reference.

[0107] The catalyst compositions used in this process produce goodquality polymer particles without substantially fouling the reactor.When the catalyst composition is to be used in a loop reactor zone underslurry polymerization conditions, it is preferred when the particle sizeof the treated solid oxide compound is in the range of about 10 to about1000 microns, preferably about 25 to about 500 microns, and mostpreferably, 50 to 200 microns, for best control during polymerization.

[0108] In a more specific embodiment of this invention, a process isprovided to produce a catalyst composition, the process comprising(optionally, “iconsisting essentially of”, or “consisting of”):

[0109] (1) contacting alumina with an aqueous solution containing nickelnitrate hexahydrate to produce a nickel-containing alumina having from 1to 3 millimoles of nickel per gram of nickel-containing alumina beforecalcining;

[0110] (2) calcining the nickel-containing alumina at a temperaturewithin a range of 400 to 700° C. for 3 to 20 hours to produce a calcinedcomposition;

[0111] (3) contacting the calcined composition with carbon tetrachloridefor 10 minutes to 30 minutes to produce a treated solid oxide compoundhaving 15 to 75% by weight chlorine based on the weight of the treatedsolid oxide compound before calcining;

[0112] (4) combining the treated solid oxide compound andbis(n-butylcyclopentadienyl) zirconium dichloride at a temperaturewithin the range of 15° C. to 50° C. to produce a mixture; and

[0113] (5) after between 1 minute and 1 hour, combining the mixture andtriethylaluminum to produce the catalyst composition.

[0114] Hydrogen can be used with this invention in a polymerizationprocess to control polymer molecular weight.

[0115] After the polymers are produced, they can be formed into variousarticles, such as, for example, household containers and utensils, filmproducts, drums, fuel tanks, pipes, geomembranes, and liners. Variousprocesses can form these articles. Usually, additives and modifiers areadded to the polymer in order to provide desired effects. It is believedthat by using the invention described herein, articles can be producedat a lower cost, while maintaining most, if not all, of the uniqueproperties of polymers produced with metallocene catalysts.

EXAMPLES Test Methods

[0116] A “Quantachrome Autosorb-6 Nitrogen Pore Size DistributionInstrument” was used to determined surface area and pore volume. Thisinstrument was acquired from the Quantachrome Corporation, Syosset, N.Y.

Preparation of Oxide Compounds for Control Runs

[0117] Silica was obtained from W. R. Grace, grade 952, having a porevolume of about 1.6 cc/g and a surface area of about 300 m²/g.

[0118] Alumina was obtained from Akzo Nobel Chemical as Ketjen grade Balumina having a pore volume of about 1.78 cc/g and a surface area ofaround 350 m²/g.

[0119] To calcine each of the oxide compounds, about 10 grams wereplaced in a 1.75 inch quartz tube fitted with a sintered quartz disk atthe bottom. While the oxide compound was supported on the disk, dry airwas blown up through the disk at the linear rate of about 1.6 to about1.8 standard cubic feet per hour. An electric firnace around the quartztube was then turned on, and the temperature was raised at the rate of400 degrees centigrade per hour to the indicated temperature, such as600° C. At that temperature, the oxide compound was allowed to fluidizefor three hours in the dry air. Afterward, the oxide compound wascollected and stored under dry nitrogen, where it was protected from theatmosphere until ready for testing. It was never allowed to experienceany exposure to the atmosphere.

Polymerization Runs

[0120] Polymerization runs were made in a 2.2 liter steel reactorequipped with a marine stirrer rumnng at 400 revolutions per minute(rpm). The reactor was surrounded by a steel jacket containing boilingmethanol with a connection to a steel condenser. The boiling point ofthe methanol was controlled by varying nitrogen pressure applied to thecondenser and jacket, which permitted precise temperature control towithin half a degree centigrade, with the help of electronic controlinstruments.

[0121] Unless otherwise stated, first, a small amount (0.01 to 0.10grams normally) of the oxide compound or the treated solid oxidecompound was charged under nitrogen to a dry reactor. Next, 2.0milliliters of a toluene solution containing 0.5 percent by weight ofbis(n-butylcyclopentadienyl) zirconium dichloride were added, followedby 0.6 liters of isobutane liquid. Then, 2.0 milliliters of a 1.0 molarsolution of triethylaluminum (TEA) were added, followed by another 0.6liters of isobutane liquid. Then, the reactor was heated up to thespecified temperature. Finally, ethylene was added to the reactor toequal a fixed pressure of about 550 psig to produce a reaction mixture.The reaction mixture was allowed to stir for usually about one hour. Asethylene was consumed, more ethylene flowed in to maintain the pressure.The activity was noted by recording the flow of ethylene into thereactor to maintain the set pressure.

[0122] After the allotted time, the ethylene flow was stopped, and thereactor slowly depressurized and opened to recover a granular polymer.In all cases, the reactor was clean with no indication of any wallscale, coating or other forms of fouling. The polymer was then removedand weighed. Activity was specified as grams of polymer produced pergram of oxide compound or treated solid oxide compound charged per hour.

[0123] Experimental Results:

[0124] Specific examples of this invention are described below. Theresults of these polymerization runs are listed in Table 1.

Example 1 (Silica)

[0125] A 0.5686 gram sample of silica calcined per the procedurediscussed previously was charged to the reactor for polymerizationtests. Two milliliters of 1.0 molar triethylaluminum were added to thereactor along with 2 milliliters of 0.5 weight percentbis(n-butylcyclopentadienyl) zirconium dichloride. During apolymerization run of 63.0 minutes, 0.65 grams of polymer were producedyielding an activity of 1 gram of polymer per gram of silica per hour.

Example 2 (Alumina)

[0126] A 0.2361 gram sample of alumina calcined per the procedurediscussed previously was charged to the reactor for polymerizationtests. Two milliliters of 1.0 molar triethylaluminum were added alongwith 2 milliliters of 0.5 weight percent bis(n-butylcyclopentadienyl)zirconium dichloride. During a polymerization run of 60.9 minutes, 6.9grams of polymer were produced yielding an activity of 29 grams ofpolymer per gram of alumina per hour.

Example 3 (ChloridedAlumina)

[0127] Ten grams of Ketjen grade B alumina were calcined in air forthree hours at 600° C. as described previously. After calcining, thefuirnace temperature was maintained at 600° C., and the gas stream waschanged from air to dry nitrogen. Then, 2.3 milliliters of carbontetrachloride were injected into the nitrogen stream and evaporatedupstream from the alumina bed. The carbon tetrachloride vapor wascarried up through the bed and reacted with the alumina to produce achlorided alumina. The chlorided alumina was white in color.

[0128] A sample of the chlorided alumina, weighing 0.2058 grams, wasthen charged to the reactor for polymerization tests. Two milliliters of1.0 molar triethylalunminum were added along with 2 milliliters of 0.5percent bis(n-butylcyclopentadienyl) zirconium dichloride. During apolymerization run of 63.0 minutes, 351.5 grams of polymer were producedyielding an activity of 1627 grams of polymer per gram of chloridedalumina per hour.

Example 4 (Chlorided, Nickel-Containing Alumina)

[0129] 27.3 grams of the Ketjen Grade B alumina were impregnated with 50milliliters of an aqueous solution containing 7.94 grams of nickelnitrate hexahydrate (or 1 mmol of nickel per gram of alumina) to yield awet sand consistency. This produced a nickel-containing alumina. Thenickel-containing alumina was dried under vacuum at 120° C. for 16hours. The nickel-containing alumina was pushed through a 100 meshscreen to produce a light green powder.

[0130] Fifty milliliters of the nickel-containing alumina, or about 14grams, were calcined in dry air for three hours at 600° C. Then, the airstream was changed to dry nitrogen, and 2.5 milliliters of carbontetrachloride were injected into the nitrogen stream under the bed ofnickel-containing alumina. The carbon tetrachloride evaporated overabout 10 minutes, and the vapors were carried up through thenickel-containing alumina bed contacting and reacting with thenickel-containing alumina to produce a chlorided, nickel-containingalunina. Then, the chlorided, nickel-containing alumina was cool andstored under nitrogen for later polymerization tests. The chlorided,nickel-containing alumina had a light blue-green color.

[0131] A sample of the chlorided, nickel-containing alumina, weighing0.1 101 grams, was then charged to the reactor for polymerization tests.Two milliliters of 1.0 molar triethylaluminum were added along with 2milliliters of 0.5 percent bis(n-butylcyclopentadienyl) zirconiumdichloride. During 41.5 minutes of a polymerization run, 281 grams ofpolymer were produced yielding an activity of 3690 grams of polymer pergram of chlorided, nickel-containing alumina per hour. TABLE 1Polymerization Results Amount Of Calcining Test Test Temp. CompoundPolymer Run Time Activity* Example Compound* (° C.) (g) (g) (min)(g/g/h) 1-Control Silica 600 0.5686 0.65 63.0 1 2-Control Alumina 6000.2361 6.9 60.9 29 3-Control Chlorided 600 0.2058 351.5 63.0 1627Alumina 4- Chlorided 600 0.1101 281 41.5 3690 Invention Nickel-Containing Alumina

[0132] While this invention has been described in detail for the purposeof illustration, it is not intended to be limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A process to produce a catalystcomposition, said process comprising contacting an organometal compound,an organoaluminum compound, and a treated solid oxide compound toproduce said catalyst composition, wherein said organometal compound hasthe following general formula: (X¹)(X²)(X³)(X⁴)M¹ wherein M¹ is selectedfrom the group consisting of titanium, zirconium, and hafnium; wherein(X¹) is independently selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls; wherein substituentson said substituted cyclopentadienyls, substituted indenyls, andsubstituted fluorenyls of (X¹) are selected from the group consisting ofaliphatic groups, cyclic groups, combinations of aliphatic and cyclicgroups, silyl groups, alkyl halide groups, halides, organometallicgroups, phosphorus groups, nitrogen groups, silicon, phosphorus, boron,germanium, and hydrogen; wherein at least one substituent on (X¹) can bea bridging group which connects (X¹) and (X²); wherein (X³) and (X⁴) areindependently selected from the group consisting of halides, aliphaticgroups, substituted aliphatic groups, cyclic groups, substituted cyclicgroups, combinations of aliphatic groups and cyclic groups, combinationsof substituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, aridogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkyloxide groups, substituted alkyloxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups; wherein (X²) is selected from thegroup consisting of cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, substituted fluorenyls,halides, aliphatic groups, substituted aliphatic groups, cyclic groups,substituted cyclic groups, combinations of aliphatic groups and cyclicgroups, combinations of substituted aliphatic groups and cyclic groups,combinations of aliphatic groups and substituted cyclic groups,combinations of substituted aliphatic groups and substituted cyclicgroups, amido groups, substituted amido groups, phosphido groups,substituted phosphido groups, alkyloxide groups, substituted alkyloxidegroups, aryloxide groups, substituted aryloxide groups, organometallicgroups, and substituted organometallic groups; wherein substituents on(X²) are selected from the group consisting of aliphatic groups, cyclicgroups, combinations of aliphatic groups and cyclic groups, silylgroups, alkyl halide groups, halides, organometallic groups, phosphorusgroups, nitrogen groups, silicon, phosphorus, boron, germanium, andhydrogen; wherein at least one substituent on (X²) can be a bridginggroup which connects (X¹) and (X²); wherein said organoaluminun compoundhas the following general formula: Al(X⁵)_(n)(X⁶)_(3−n) wherein (X⁵) isa hydrocarbyl having from 1 to about 20 carbon atoms; wherein (X⁶) is ahalide, hydride, or alkoxide; and wherein “n” is a number from 1 to 3inclusive; wherein said treated solid oxide compound comprises nickel, ahalogen, and a solid oxide compound; wherein said halogen is selectedfrom the group consisting of chlorine or bromine; wherein said solidoxide compound is selected from the group consisting of alumina,aluninophosphate, aluminosilicate, and mixtures thereof:
 2. A process toproduce a catalyst composition, said process comprising: 1) contactingalumina with an aqueous solution containing nickel nitrate hexahydrateto produce a nickel-containing alumina having from 1 to 3 millimoles ofnickel per gram of nickel-containing alumina before calcining; 2)cacining said nickel-containing alumina at a temperature within a rangeof 400 to 700° C. for 3 to 20 hours to produce a calcined composition;3) contacting said calcined composition with carbon tetrachloride for 10minutes to 30 minutes to produce a treated solid oxide compound havingfrom 15 to 75% by weight chlorine based on the weight of the treatedsolid oxide compound before calcining; 4) combining said treated solidoxide compound and bis(n-butylcyclopentadienyl) zirconium dichloride ata temperature within a range of 15° C. to 50° C. to produce a mixture;and 5) after between 1 minute and 1 hour, combining said mixture andtriethylaluminum to produce said catalyst composition.
 3. A processaccording to claim 2 wherein said process consists essentially of steps(1), (2), (3), (4), and (5).
 4. A catalyst composition produced by saidprocess of claim
 1. 5. A catalyst composition according to claim 4wherein said catalyst composition has an activity greater than 2000under slurry polymerization conditions, using isobutane as a diluent,with a polymerization temperture of 90° C., and an ethylene pressure of550 psig.
 6. A process according to claim 5 wherein said catalystcomposition has an activity greater than 3000 under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 7. A catalyst composition according to Claiun 5 wherein a weightratio of said organoaluminum compound to said treated solid oxidecompound in said catalyst composition ranges from about 3:1 to about1:100.
 8. A catalyst composition according to claim 7 wherein saidweight ratio of said organoaluminum compound to said treated solid oxidecompound in said catalyst composition ranges from 1:1 to 1:50.
 9. Acatalyst composition according to claim 5 wherein a weight ratio of saidtreated solid oxide compound to said organometal compound in saidcatalyst composition ranges from about 1000:1 to about 10:1.
 10. Acatalyst composition according to claim 9 wherein said weight ratio ofsaid treated solid oxide compound to said organometal compound in saidcatalyst composition ranges from 250:1 to 20:1.
 11. A catalystcomposition according to claim 10 wherein said treated solid oxidecompound comprises alumina, 1 to 3 millimoles of nickel per gram ofalumina, from 4 to 20% by weight chlorine based on the weight of saidtreated solid oxide compound before calcining, and is calcined for 3 to20 hours at a temperature from 400 to 700° C.
 12. A catalyst compositioncomprising a post-contacted organometal compound, a post-contactedorganoaluminum compound, and a post-contacted treated solid oxidecompound.
 13. A polymerization process comprising contacting at leastone monomer and said catalyst composition of claim 4 underpolymerization conditions to produce a polymer.
 14. A process accordingto claim 13 wherein said polymerization conditions comprise slurrypolymerization conditions.
 15. A process according to claim 14 whereinsaid contacting is conducted in a loop reaction zone.
 16. A processaccording to claim 15 wherein said contacting is conducted in thepresence of a diluent that comprises, in major part, isobutane.
 17. Aprocess according to claim 13 wherein at least one monomer is ethylene.18. A process according to claim 13 wherein at least one monomercomprises ethylene and an aliphatic 1-olefm having 3 to 20 carbon atomsper molecule.
 19. An article that comprises said polymer producedaccording to claim 13.